The JAXA Hayabusa2 mission returned well-preserved samples collected from the carbonaceous asteroid Ryugu, providing unique non-terrestrially weathered samples from a known parent body. This work aims to provide a better understanding of the formation and evolution of primitive asteroidal matter by studying the fine scale association of organic matter and minerals in Ryugu samples. We characterized the samples by IR nanospectroscopy using the AFM-IR technique. This technique overcomes the diffraction limit (of several microns) of conventional infrared microspectroscopy (µ-FTIR). The samples were mapped in the mid-IR range at a lateral spatial resolution about a hundred times better than with µ-FTIR. This provided us with unique in situ access to the distribution of the different infrared signatures of organic components at the sub-micron scale present in the Ryugu whole-rock samples as well as to the characterization of the compositional variability of Ryugu in the insoluble organic matter (IOM) chemically extracted from the Ryugu samples. The AFM-IR maps of whole-rock particles and IOM residues from Ryugu samples were recorded with a lateral resolution of tens of nanometers. Spectra were recorded in the 1900-900 cm$^−1$ spectral range by AFM-IR (Icon-IR) for all samples, and additional spectra were recorded from 2700 to 4000 cm$^−1$ for one IOM sample by an optical photothermal IR (O-PTIR) technique using a mIRage$^ textregistered $ IR microscope. Organic matter is present in two forms in the whole-rock samples: as a diffuse phase intermixed with the phyllosilicate matrix and as individual organic nanoparticles. We identify the Ryugu organic nanoparticles as nanoglobule-like inclusions texturally resembling nanoglobules present in primitive meteorites. Using AFM-IR, we record for the first time the infrared spectra of Ryugu organic nanoparticles that clearly show enhanced carbonyl (C=O) and CH contributions with respect to the diffuse organic matter in Ryugu whole-rock and IOM residue.

Abstract

Transmission electron microscopy analyses of Hayabusa2 samples show that Ryugu organic matter exhibits a range of morphologies, elemental compositions, and carbon functional chemistries consistent with those of carbonaceous chondrites that have experienced low‐temperature aqueous alteration. Both nanoglobules and diffuse organic matter are abundant. Non‐globular organic particles are also present, and including some that contain nanodiamond clusters. Diffuse organic matter is finely distributed in and around phyllosilicates, forms coatings on other minerals, and is also preserved in vesicles in secondary minerals such as carbonate and pyrrhotite. The average elemental compositions determined by energy‐dispersive spectroscopy of extracted, demineralized insoluble organic matter samples A0107 and C0106 are C₁₀₀N₃O₉S₁ and C₁₀₀N₃O₇S₁, respectively, with the difference in O/C slightly outside the difference in the standard error of the mean. The functional chemistry of the nanoglobules varies from mostly aromatic C=C to mixtures of aromatic C=C, ketone C=O, aliphatic (CH_n), and carboxyl (COOH) groups. Diffuse organic matter associated with phyllosilicates has variable aromatic C, ketone and carboxyl groups, and some localized aliphatics, but is dominated by molecular carbonate (CO₃) absorption, comparable to prior observations of clay‐bound organic matter in CI meteorites.

Abstract

Ferromanganese (Fe‐Mn) nodules are widely considered significant economic potential and paleoenvironmentally significant archives. Generally, submicron‐thick layers (SMLs) are basic units of the Fe‐Mn nodules and record valuable information about the environment of Fe‐Mn nodule formation, but their structural, mineralogical, and chemical features are not well resolved. Here, we investigated a typical hydrogenetic Fe‐Mn nodule from the Penrhyn Basin in the South Pacific Ocean, using various microanalytical techniques. The nodule mainly consists of a micronodule‐dominant region around the core, a crust near the surface with Mn‐ and Fe‐rich layers, and stromatolite‐like textures between them. These textures are composed of distinct and indistinct SMLs parallel to their growth front. Although the distinct and indistinct SMLs have different mineral phases, the transmission electron microscopy revealed that these layered structures are actually interstratification of SMLs with different crystal sizes of foliated phyllomanganates. Large crystals contain higher Mn oxidation states than small crystals. Such variations of Mn oxidation state with different crystal sizes along the growth direction imply the short‐term regular fluctuation in the redox condition of the Lower Circumpolar Deep Water.

Abstract

We report a Fourier transform infrared analysis of functional groups in insoluble organic matter (IOM) extracted from a series of 100–500 μm Ryugu grains collected during the two touchdowns of February 22 and July 11, 2019. IOM extracted from most of the samples is very similar to IOM in primitive CI, CM, and CR chondrites, and shows that the extent of thermal metamorphism in Ryugu regolith was, at best, very limited. One sample displays chemical signatures consistent with a very mild heating, likely due to asteroidal collision impacts. We also report a lower carbonyl abundance in Ryugu IOM samples compared to primitive chondrites, which could reflect the accretion of a less oxygenated precursor by Ryugu. The possible effects of hydrothermal alteration and terrestrial weathering are also discussed. Last, no firm conclusions could be drawn on the origin of the soluble outlier phases, observed along with IOM in this study and in the preliminary analysis of Ryugu samples. However, it is clear that the HF/HCl residues presented in this publication are a mix between IOM and the nitrogen‐rich outlier phase.

Abstract

More than a decade has passed since the Fukushima nuclear accident in 2011 and contamination around the nuclear power plant is primarily caused by ¹³⁷Cs. One of the materials retaining radiocesium in the environment is radiocesium-bearing silicate glass microparticles (CsMPs), which have not been reported in previous nuclear accidents. Although the prediction of environmental fates of CsMPs is of interest because of their extremely high specific radioactivity, knowledge about their physicochemical properties is still limited. Here we show that the dissolution behavior of CsMPs is comparable to that of silica-rich glass and significantly depends on the surrounding environment. CsMP dissolution experiments were conducted in solutions with various solute components and pH levels at 60 °C. In neutral and basic solutions, the estimated dissolution rate was accelerated by alkali ions such as Na⁺, which is known to play a catalytic role for the dissolution of silica. In contrast, the dissolution in acid was slow even in the presence of alkali ions. The dissolution under acid conditions was possibly retarded by a thin amorphous silica layer formed on the CsMP surfaces. Such characteristics of the dissolution are consistent with that of silica-rich glass. To infer the dissolution behavior of CsMPs in the human body, the dissolution rate in Ringer’s solution at 37 °C was estimated as 1.00 ± 0.37 μm/year.

<jats:p><jats:italic>Context.</jats:italic> The current period is conducive to exploring our Solar System's origins with recent and future space sample return missions, which provide invaluable information from known Solar System asteroids and comets The Hayabusa2 mission of the Japan Aerospace Exploration Agency (JAXA) recently brought back samples from the surface of the Ryugu carbonaceous asteroid.</jats:p>
<jats:p><jats:italic>Aims.</jats:italic> We aim to identify the different forms of chemical composition of organic matter and minerals that constitute these Solar System primitive objects, to shed light on the Solar System's origins.</jats:p>
<jats:p><jats:italic>Methods.</jats:italic> In this work, we recorded infrared (IR) hyper-spectral maps of whole-rock Ryugu asteroid samples at the highest achievable spatial resolution with a synchrotron in the mid-IR (MIR). Additional global far-IR (FIR) spectra of each sample were also acquired.</jats:p>
<jats:p><jats:italic>Results.</jats:italic> The hyper-spectral maps reveal the variability of the functional groups at small scales and the intimate association of phyl-losilicates with the aliphatic components of the organic matter present in Ryugu. The relative proportion of column densities of the identified IR functional groups (aliphatics, hydroxyl + interlayer and/or physisorbed water, carbonyl, carbonates, and silicates) giving access to the composition of the Ryugu samples is estimated from these IR hyper-spectral maps. Phyllosilicate spectra reveal the presence of mixtures of serpentine and saponite. We do not detect anhydrous silicates in the samples analysed, at the scales probed. The carbonates are dominated by dolomite. Aliphatics organics are distributed over the whole samples at the micron scale probed with the synchrotron, and intimately mixed with the phyllosilicates. The aromatic C=C contribution could not be safely deconvolved from OH in most spectra, due to the ubiquitous presence of hydrated minerals. The peak intensity ratios of the organics methylene to methyl (CH<jats:sub>2</jats:sub>/CH<jats:sub>3</jats:sub>) of the Ryugu samples vary between about 1.5 and 2.5, and are compared to the ratios in chondrites from types 1 to 3. Overall, the mineralogical and organic characteristics of the Ryugu samples show similarities with those of CI chondrites, although with a noticeably higher CH<jats:sub>2</jats:sub>/CH<jats:sub>3</jats:sub> in Ryugu than generally measured in C1 chondrites collected on Earth, and possibly a higher carbonate content.</jats:p>

Samples of the carbonaceous asteroid (162173) Ryugu were collected and brought to Earth by the Hayabusa2 spacecraft. We investigated the macromolecular organic matter in Ryugu samples and found that it contains aromatic and aliphatic carbon, ketone, and carboxyl functional groups. The spectroscopic features of the organic matter are consistent with those in chemically primitive carbonaceous chondrite meteorites that experienced parent-body aqueous alteration (reactions with liquid water). The morphology of the organic carbon includes nanoglobules and diffuse carbon associated with phyllosilicate and carbonate minerals. Deuterium and/or nitrogen-15 enrichments indicate that the organic matter formed in a cold molecular cloud or the presolar nebula. The diversity of the organic matter indicates variable levels of aqueous alteration on Ryugu’s parent body.

Abstract

The infrared spectral characteristics of organic‐rich acid residues prepared from Ryugu samples returned by the JAXA Hayabusa2 mission generally match those from unheated carbonaceous chondrite meteorites, but the residues from Ryugu are richer in methyl and methylene functional groups and have higher CH₂/CH₃ ratios. Moreover, two distinct outlier carbonaceous phases are found; one with spectral characteristics of N‐H functional groups, likely amides, and a second phase containing less nitrogen. Such infrared characteristics of Ryugu organic matter might indicate the pristine nature of the freshly collected samples and reflect the near‐surface chemistry in the parent asteroid.

We have conducted a NanoSIMS-based search for presolar material in samples recently returned from C-type asteroid Ryugu as part of JAXA's Hayabusa2 mission. We report the detection of all major presolar grain types with O- and C-anomalous isotopic compositions typically identified in carbonaceous chondrite meteorites: 1 silicate, 1 oxide, 1 O-anomalous supernova grain of ambiguous phase, 38 SiC, and 16 carbonaceous grains. At least two of the carbonaceous grains are presolar graphites, whereas several grains with moderate C isotopic anomalies are probably organics. The presolar silicate was located in a clast with a less altered lithology than the typical extensively aqueously altered Ryugu matrix. The matrix- normalized presolar grain abundances in Ryugu are 4.8(-2.6)(+4.7) ppm for O-anomalous grains, 25(-)(5)(+)(6) ppm for SiC grains, and 11(-3)(+5) ppm for carbonaceous grains. Ryugu is isotopically and petrologically similar to carbonaceous Ivuna-type (CI) chondrites. To compare the in situ presolar grain abundances of Ryugu with CI chondrites, we also mapped Ivuna and Orgueil samples and found a total of 15 SiC grains and 6 carbonaceous grains. No O-anomalous grains were detected. The matrix-normalized presolar grain abundances in the CI chondrites are similar to those in Ryugu: 23(-6)(+7) ppm SiC and 9.0 (+5.4)(-3)(.6) ppm carbonaceous grains. Thus, our results provide further evidence in support of the Ryugu-CI connection. They also reveal intriguing hints of small-scale heterogeneities in the Ryugu samples, such as locally distinct degrees of alteration that allowed the preservation of delicate presolar material.

© 2020, The Author(s). Radiocaesium-bearing microparticles (CsMPs), which are substantially silicate glass, were formed inside the damaged reactor and released to the environment by the Fukushima Dai-ichi Nuclear Power Plant accident in March 2011. The present study reports several valuable findings regarding their composition and structure using advanced microanalytical techniques. X-ray absorption near-edge structure of Fe L3-absorption indicated that the oxidation state of the iron dissolved in the glass matrix of the CsMPs was originally nearly divalent, suggesting that the atmosphere in which the CsMPs were formed during the accident was considerably reductive. Another major finding is that sodium, which has not been recognised as a constituent element of CsMPs thus far, is among the major elements in the glass matrix. The atomic percent of Na is higher than that of other alkali elements such as K and Cs. Furthermore, halite (NaCl) was found as an inclusion inside a CsMP. The existence of Na in CsMPs infers that seawater injected for cooling might reach the inside of the reactor before or during the formation of the CsMPs. These results are valuable to infer the environment inside the reactor during the accident and the debris materials to be removed during the decommissioning processes.

<p>福島の環境回復のためには放射性Csで汚染された大量の除去土壌の減容化が必要である。我々は、従来の熱処理よりも300℃以上低い処理温度で土壌除染を可能にするセシウムフリー鉱化法(CFM)を提案している。CFMではアルカリ塩などの反応剤との化学反応により生じる土壌中の粘土鉱物の分解と相変態を通してCsを除去し、熱処理で得られた生成物の産業利用により除去土壌を減容化することを目指しているが、熱処理には反応剤の種類・量、温度、圧力、雰囲気、処理時間など様々な因子が関与するため、その最適化のためには系統的研究が必要不可欠である。本研究ではCaCl₂, MgCl₂, KCl, NaClの4種類の塩化物試薬を反応剤に用いて熱処理を行い、大気条件と低圧条件では除染率と生成物が異なることを見いだした。さらに、得られた知見に基づき、海水塩を用いた熱処理について提案する。</p>

Since a three-dimensional (3D) cellular ultrastructure is significant for biological functions, it has been investigated using various electron microscopic techniques. Although transmission electron microscopy (TEM)-based techniques are traditionally used, cells must be embedded in resin and sliced into ultrathin sections in sample preparation processes. Block-face observation using a scanning electron microscope (SEM) has also been recently applied to 3D observation of cellular components, but this is a destructive inspection and does not allow re-examination. Therefore, we developed electron tomography using a transmission electron imaging technique called Plate-TEM. With Plate-TEM, the cells cultured directly on a scintillator plate are inserted into a conventional SEM equipped with a Plate-TEM observation system, and their internal structures are observed by detecting scintillation light produced by electrons passing through the cells. This technology has the following four advantages. First, the cells cultured on the plate can be observed at electron-microscopic resolution since they remain on the plate. Second, both surface and internal information can be obtained simultaneously by using electron- and photo-detectors, respectively, because a Plate-TEM detector is installed in an SEM. Third, the cells on the scintillator plate can also be inspected using light microscopy because the plate has transparent features. Finally, correlative observation with other techniques, such as conventional TEM, is possible after Plate-TEM observation because Plate-TEM is a non-destructive analysis technique. We also designed a sample stage to tilt the samples for tomography with Plate-TEM, by which 3D organization of cellular structures can be visualized as a whole cell. In the present study, Mm2T cells were investigated using our tomography system, resulting in 3D visualization of cell organelles such as mitochondria, lipid droplets, and microvilli. Correlative observations with various imaging techniques were also conducted by successive observations with light microscopy, SEM, Plate-TEM, and conventional TEM. Consequently, the Plate-TEM tomography technique encourages understanding of cellular structures at high resolution, which can contribute to cellular biological research.

Biomineralization, in which organisms create biogenic hard tissues, with hardness or flexibility enhanced by organic inorganic interaction is an interesting and attractive focus for application of biomimetic functional materials. Calcites in the prismatic layer of Pinctada fucata are tougher than abiotic calcites due to small crystal defects. However, the molecular mechanism of the defect formation remains unclear. Here, chitin and two chitinolytic enzymes, chitinase and chitobiase, were identified as organic matrices related to for the formation of small crystal defects in the prismatic layer. Experiments with a chitinase inhibitor in vivo showed chitinase is necessary to form the prismatic layer. Analysis of calcite crystals, which were synthesized in a chitin hydrogel treated with chitinolytic enzymes, by electron microscopy and X-ray diffraction showed that crystal defects became larger as chitin was more degraded. These results suggest that interactions between chitin and calcium carbonate increase as chitin is thinner. (C) 2017 Published by Elsevier Inc.

To investigate the sorption mechanism of cesium (Cs) into clay minerals, high-resolution (scanning) transmission electron microscopy (TEM/STEM) imaging of Cs in mica (phlogopite) has been conducted. Platy phlogopite powders were immersed in a cesium chloride (CsCl) solution to achieve Cs+-K+ ion-exchange at the interlayer regions in phlogopite. To observe many phlogopite particles with the incident electron beam parallel to the mica layers, cross-sectional thin specimens were prepared from sedimented particles using a focused ion beam. High-angle annular dark-field imaging with STEM is superior to conventional high-resolution TEM (HRTEM) for visualizing Cs at interlayer sites even in thicker crystal regions and/or at lower magnification due to the intense Z-contrast of Cs. However, HRTEM is also practical for estimating the concentration of Cs at the interlayer site from the thickness dependence of the contrast at the interlayer region. Cs sorption of micas was previously thought to be localized mainly at the frayed-edge sites of mica crystals. However, the present observations indicate that Cs substitution of K occurs not around crystal edges but deep inside the crystals along specific interlayer regions.

It is widely accepted that organic substances regulate or influence the structure of biominerals, but its direct evidences are not plenty. Here we show that the crystallographic microstructures in biotic calcites arise from incorporated intracrystalline organic molecules (IOMs), through a comparison between biotic calcites in shells and synthetic ones with the IOMs extracted from the shells. Although the prismatic layers of a pearl oyster (Pinctada fucata) and a pen shell (Atrina pectinata) morphologically resemble eact other, the crystallographic features of constituent calcites are considerably differnet; in Pinctada, the IOMs are distributed inhomogeneously to form small-angle grain boundaries and associated crystal defects, whereas in Atrina, the IOMs are distributed almost homogeneously and defects are rare in the calcite crystals. We conducted in vitro calcite syntheses in the presence of the IOMs in EDTA-soluble extracts from the prisms. The IOMs in the extracts from Pinctada and Atrina were incorporated into synthetic calcites in a different manner, exhibiting defect-rich/free features as observed in the nature shells. With regard to amino acid compositions of the IOMs. the extract from Atrina has a higher proportion of acidic amino acids than that from Pinctada, implying that acidic proteins do not correlate directly to their affinity for aclcium carbonate crystals. (C) 2013 Elsevier B.V. All rights reserved.

The influence of intracrystalline organic macromolecules on the microstructure and properties of host crystals has been investigated by micro- and macroscopic analyses for several biogenic calcites: prisms in the outer layers of pearl oysters (Pinctada fucata), oysters (Crassostrea nippona), and pen shells (Atrina pectinata); folia in the inner layers of C. nippona and scallops (Patinopecten yessoensis); and coccoliths of Pleurochrysis carterae. Thermogravimetric analysis showed that the three prisms contain more intracrystalline organic matter than the folia and coccolith. Transmission electron microscopy (TEM) revealed that Fresnel contrasts, which probably correspond to the intracrystalline organic macromolecules, are distributed inhomogeneously and partition the calcite crystals into subgrains with small misorientations in the prisms of P. fucata and C. nippona. From peak broadening in powder X-ray diffraction (XRD), we found a large variance of lattice spacing (Delta d/d) in the two prisms. On the other hand, intracrystalline macromolecules in the prisms of A. pectinata are distributed rather homogeneously and do not influence the crystal structure, as revealed by diffraction contrast in TEM. XRD of the prisms in A. pectinata indicates significantly smaller Delta d/d than that for the other two prisms. In the folia and coccolith, intracrystalline macromolecules were scarcely observed in TEM, and the estimated Delta d/d is small.

As a crucial first step for understanding the organic-inorganic interaction in biomineralization of mollscan shells, localization of the intracrystalline organic macromolecules in biogenic calcium carbonate crystals of the nacreous, prismatic (Pinctada fucata) and foliated (Cellana toreuma) microstructures were investigated using Fresnel contrast analysis in a transmission electron microscope. Spherular Fresnel contrasts in the crystals correspond to organic substances, which was confirmed by the detection of 1s -&gt; m* (C=C) transition peak at 284 eV in electron energy loss spectroscopy. Nanosized (5-10 nm) spherules in the aragonite tablets constituting the nacreous layer of P. fucata specifically concentrate in the vicinity of the interlamellar membrane between the aragonite tablets. The dominant sizes of the organic macromolecules extracted by dissolving the aragonite tablets in the nacreous layer of P. fucata were estimated using the gel-filtration analysis to be roughly 10 and 4 nm, which dimensionally corresponds to the sizes observed by Fresnel contrast imaging in the tablets. These results will serve for understanding the functions of intracrystalline organic macromolecules in mollusk shells. (C) 2011 Elsevier B.V. All rights reserved.

The fine structure of the calcite prism in the outer layer of a pearl oyster, Pinctada fucata, has been investigated using various electron beam techniques, in order to understand its characteristics and growth mechanism including the role of intracrystalline organic substances. As the calcite prismatic layer grows thicker, sinuous boundaries develop to divide the prism into a number of domains. The crystal misorientation between the adjacent domains is several to more than ten degrees. The component of the misorientation is mainly the rotation about the c-axis. There is no continuous organic membrane at the boundaries. Furthermore, the crystal orientation inside the domains changes gradually, as indicated by the electron back-scattered diffraction (EBSD) in a scanning electron microscope (SEM). Transmission electron microscopy (TEM) examination revealed that the domain consists of sub-grains of a few hundred nanometers divided by small-angle grain boundaries, which are probably the origin of the gradual change of the crystal orientation inside the domains. Spherular Fresnel contrasts were often observed at the small-angle grain boundaries, in defocused TEM images. Electron energy-loss spectroscopy (EELS) indicated the spherules are organic macromolecules, suggesting that incorporation of organic macromolecules during the crystal growth forms the sub-grain structure of the calcite prism. (c) 2010 Elsevier Ltd. All rights reserved.